WO2024082735A1 - Organic-inorganic composite toughening material and use thereof in concrete - Google Patents

Organic-inorganic composite toughening material and use thereof in concrete Download PDF

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Publication number
WO2024082735A1
WO2024082735A1 PCT/CN2023/108309 CN2023108309W WO2024082735A1 WO 2024082735 A1 WO2024082735 A1 WO 2024082735A1 CN 2023108309 W CN2023108309 W CN 2023108309W WO 2024082735 A1 WO2024082735 A1 WO 2024082735A1
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Prior art keywords
concrete
organic
inorganic composite
toughening material
initiator
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PCT/CN2023/108309
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French (fr)
Chinese (zh)
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汤金辉
徐洁
高畅
王瑞
王文彬
舒鑫
韩方玉
刘加平
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东南大学
江苏苏博特新材料股份有限公司
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Publication of WO2024082735A1 publication Critical patent/WO2024082735A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/04—Acids; Metal salts or ammonium salts thereof
    • C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]

Definitions

  • the invention relates to the technical field of building materials, and in particular to an organic-inorganic composite toughening material and application thereof in concrete.
  • Concrete is the most widely used and largest-volume civil engineering material, but it has poor toughness, low ductility, is easy to crack, and has large shrinkage upon drying, which seriously affects the overall safety and service life of buildings.
  • Concrete toughening includes fiber toughening and matrix toughening.
  • the former is costly and has poor practical application effects, while the latter is mainly achieved by adding polymers and nano-modified materials.
  • Polymer concrete has high toughness and flexural strength, but the addition of polymers often leads to a significant decrease in compressive strength.
  • the introduction of inorganic nanomaterials into concrete can improve the microstructure of the matrix and interface transition zone, reduce porosity, and reduce the occurrence of cracks, but the actual toughening effect is not obvious.
  • Patent CN111517703A High Flexural Cement-Based Material and Preparation Method thereof discloses a high flexural cement-based material.
  • the invention uses initiators and accelerators to form polymers in the cement hydration process and chemically bonds with cement hydrates, so that the 28-day flexural strength of cement paste is increased by 64% to 220%, and the compressive strength is reduced by 1% to 32%.
  • the 28-day flexural strength of the cement mortar prepared in this scheme is increased by up to 46%, and the corresponding compressive strength is reduced by 37%.
  • this method has not been studied for more complex concrete systems, and the effect is still unclear.
  • Patent CN109250963B "A composite toughened concrete and its preparation method" discloses a composite toughened concrete.
  • This invention uses boron nitride, which has excellent toughening performance, as a base material as a concrete additive, giving the concrete good microscopic interface bonding, toughness and fatigue resistance, and the prepared concrete can achieve a 28-day compressive strength of 30-60MPa.
  • boron nitride not only increases the production cost of concrete, but also has poor operability in actual engineering, which limits its promotion and application in actual engineering. use.
  • the present invention provides an organic-inorganic composite toughening material and its application in concrete.
  • the present invention provides an organic-inorganic composite toughening material, including a polymerizable monomer, a crosslinking agent, an initiator and a micro-interface strengthening agent;
  • the initiator accounts for 2% to 7% of the mass of the polymerized monomer
  • the crosslinker accounts for 0.05% to 0.15% of the mass of the polymerized monomer
  • the micro-interface strengthener accounts for 20% to 100% of the mass of the polymerized monomer
  • the polymerizable monomer is selected from any one or more of acrylamide, acrylate and methacrylate;
  • the micro interface strengthening agent is selected from any one or more of nano-wollastonite, calcium carbonate whisker, and calcium sulfate whisker.
  • the initiator of the present invention is an inorganic peroxide, specifically selected from a mixture of any one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
  • the crosslinking agent is selected from any one or more of N,N'-methylenebisacrylamide, 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane, divinylbenzene, and diisocyanate.
  • the present invention provides the application of the above-mentioned organic-inorganic composite toughening material in concrete, which can be applied to concrete of various strength grades to ensure the toughening effect of concrete without affecting the compressive strength.
  • the polymerized monomers in the organic-inorganic composite toughening material are polymerized in situ in cement concrete under the action of an initiator and a cross-linking agent to form a high molecular polymer, wherein the polymerized monomers account for 1% to 5% of the mass of the cement.
  • the concrete of the present invention is preferably C30 concrete.
  • the present invention also provides a method for preparing concrete containing the above-mentioned organic-inorganic composite toughening material, comprising the following steps:
  • step (3) Add water, the three solutions obtained in step (1) and the concrete to the mixture obtained in step (2); The agent is added and stirred for 3 to 9 minutes to obtain the concrete of the present invention.
  • the concrete of the present invention is a mixture of any one or more of Portland cement, ordinary Portland cement and white Portland cement with an excellent strength grade of 32.5 or above;
  • the fine aggregate in the concrete of the present invention is preferably a continuously graded sand with a particle size of 0.075 to 4.75 mm, selected from any one or more of quartz sand, river sand, garnet sand, and high-strength machine-made sand;
  • the coarse aggregate in the concrete of the present invention is preferably any one of granite, diabase, basalt and limestone, and the particle size is 4.75-9.5 mm;
  • the concrete admixture in the concrete of the present invention is preferably a mixture of any one or more of a polycarboxylate water reducer, an organosilicon defoamer, and a polyether defoamer.
  • the present invention has the following beneficial effects:
  • the present invention effectively improves the toughness of concrete through the combined action of in-situ polymerization of polymer monomers under the presence of an initiator and a cross-linking agent and a micro-interface strengthener;
  • the organic-inorganic composite toughening material of the present invention is used.
  • the polymer network structure formed by the in-situ polymerization of the polymer monomer in the cement concrete under the action of the initiator and the cross-linking agent is bonded together with the various components of the concrete, which significantly improves the bending stress of the concrete and reduces the generation of cracks;
  • the micro-interface strengthener can optimize the interface transition zone between the matrix and the aggregate, causing crack deflection, so that the 28-day compressive strength is basically not lost;
  • the concrete made by using the composite toughening material of the present invention improves the bending stress and fracture energy without affecting or reducing the compressive strength, thereby improving the problems of low flexural strength and poor toughness of existing concrete materials;
  • the bending stress of C30 concrete produced by the technology of the present invention can be increased by about 40%, and the fracture energy can be increased by about 103%.
  • An organic-inorganic composite toughening material comprising a polymer monomer, a cross-linking agent, an initiator and a micro-interface strengthening agent;
  • the polymerizable monomer is acrylamide
  • micro-interface strengthening agent is nano-wollastonite
  • the initiator is ammonium persulfate
  • the cross-linking agent is N,N'-methylenebisacrylamide.
  • An organic-inorganic composite toughening material comprising a polymerizable monomer, a crosslinking agent, an initiator and a micro-interface strengthening agent;
  • the polymerizable monomer is acrylate
  • the micro interface strengthening agent is calcium carbonate whisker
  • the initiator is potassium persulfate
  • the cross-linking agent is 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane.
  • An organic-inorganic composite toughening material comprising a polymer monomer, a cross-linking agent, an initiator and a micro-interface strengthening agent;
  • the polymerizable monomer is methacrylate
  • the micro interface strengthening agent is calcium sulfate whisker
  • the initiator is sodium persulfate
  • the crosslinking agent is a mixture of divinylbenzene and diisocyanate in a mass ratio of 1:1.
  • An organic-inorganic composite toughening material comprising a polymerizable monomer, a crosslinking agent, an initiator and a micro-interface strengthening agent;
  • the polymerizable monomer is acrylamide
  • micro-interface strengthening agent is nano-wollastonite
  • the initiator is ammonium persulfate
  • the cross-linking agent is N,N'-methylenebisacrylamide.
  • cement in each embodiment and comparative example is P ⁇ II52.5 silicate cement.
  • the "fine aggregate" in each embodiment and comparative example is river sand with a particle size of 0.075-4.75 mm continuously graded sand.
  • the "coarse aggregate" in each embodiment and comparative example is limestone, and the particle size is 4.75-9.5 mm.
  • the "concrete admixtures" in each embodiment and comparative example are polycarboxylic acid high-performance water reducing agent and silicone defoaming agent, the micro-interface strengthener added to the concrete in comparative examples 2 and 3 is nano-wollastonite, the polymerization monomer in comparative examples 4 to 7 is acrylamide, the initiator in comparative examples 5 to 7 is ammonium persulfate, and the cross-linking agent in comparative examples 6 and 7 is N,N'-methylenebisacrylamide.
  • Table 1 Concrete component contents in various embodiments and comparative examples
  • Comparative Example 1 is a basic concrete without any component of the composite toughening material added.
  • Example 2 the amount of initiator used is increased.
  • Example 3 the dosage of the micro-interface strengthening agent is increased.
  • the polymerized monomer and the crosslinking agent are mixed with water and stirred, the initiator is separately mixed with water and stirred, and the micro-interface strengthener is separately mixed with water and stirred into a suspension, and the cement, fine aggregate and coarse aggregate are mixed in a horizontal shaft or vertical shaft planetary forced mixer for 5 minutes, and then the above-mentioned three solutions, water reducer and defoamer are added to the obtained mixture and stirred for three minutes to obtain the concrete.
  • the mixture is subjected to the fresh mix performance test, it is poured into the mold for 24 hours and the mold is folded, and the comprehensive performance is tested after being placed in a standard curing environment for 3 days, 7 days and 28 days.
  • Comparative Example 1 is a benchmark C30 concrete, which has relatively low flexural stress and relatively high compressive strength.
  • micro-interface strengthener in Comparative Example 2 is beneficial to the improvement of the compressive strength of concrete; and the early fracture energy is significantly improved, but in the later stage it is basically the same as that of Comparative Example 1.
  • Comparative Example 3 After the micro-interface strengthener was further introduced in Comparative Example 3, the compressive strength of the concrete was further improved; the flexural stress was reduced to varying degrees, but the early fracture energy was significantly improved, and the later period was basically the same as that of Comparative Example 1.
  • the initiator causes the polymerizable monomer to undergo in-situ polymerization in the matrix, the bending stress is improved, and the fracture energy is greatly improved; however, the compressive strength is improved relative to Comparative Example 4, but compared with Comparative Example 1, there is still a downward trend.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

An organic-inorganic composite toughening material, comprising a polymerization monomer, a cross-linking agent, an initiator and a micro-interface enhancer, wherein the polymerization monomer is selected from any one or a mixture of acrylamide, an acrylate and a methacrylate; and the micro-interface enhancer is selected from any one or a mixture of nano-wollastonite, calcium carbonate whiskers and calcium sulfate whiskers. When the organic-inorganic composite toughening material is used in concrete, the polymerization monomer is polymerized in situ in the cement concrete under the action of the initiator and the cross-linking agent to form a high-molecular polymer, wherein the polymerization monomer accounts for 1-5% of the mass of the cement. A concrete prepared from the composite toughening material has an improved bending stress resistance and fracture resistance performance without affecting or reducing the compressive strength, thereby improving the problems of low flexural strength, poor toughness, etc., of existing concrete materials.

Description

一种有机-无机复合增韧材料及其在混凝土中的应用An organic-inorganic composite toughening material and its application in concrete 技术领域Technical Field
本发明涉及建筑材料技术领域，特别涉及一种有机-无机复合增韧材料及其在混凝土中的应用。The invention relates to the technical field of building materials, and in particular to an organic-inorganic composite toughening material and application thereof in concrete.
背景技术Background technique
混凝土作为用途最广、用量最大的土木工程材料，其韧性差、延性小、易开裂、干燥收缩大，从而严重影响建筑物的整体安全和服役寿命。Concrete is the most widely used and largest-volume civil engineering material, but it has poor toughness, low ductility, is easy to crack, and has large shrinkage upon drying, which seriously affects the overall safety and service life of buildings.
混凝土增韧包括纤维增韧和基体增韧，前者成本高且实际应用效果较差，后者主要通过加入聚合物和纳米改性材料来实现。聚合物混凝土具有较高的韧性和抗折强度，但是聚合物的加入往往会导致抗压强度的显著降低。在混凝土中引入无机纳米材料可以改善基体和界面过渡区的微观结构，降低孔隙率，减少裂缝的产生，但实际增韧效果不明显。Concrete toughening includes fiber toughening and matrix toughening. The former is costly and has poor practical application effects, while the latter is mainly achieved by adding polymers and nano-modified materials. Polymer concrete has high toughness and flexural strength, but the addition of polymers often leads to a significant decrease in compressive strength. The introduction of inorganic nanomaterials into concrete can improve the microstructure of the matrix and interface transition zone, reduce porosity, and reduce the occurrence of cracks, but the actual toughening effect is not obvious.
因此，在保证混凝土抗压强度的前提下，发明高效的混凝土增韧材料具有重要意义。Therefore, it is of great significance to invent efficient concrete toughening materials while ensuring the compressive strength of concrete.
专利CN111517703A“高抗折水泥基材料及其制备方法”，公开了一种高抗折水泥基材料。该发明通过引发剂和加速剂使聚合单体在水泥水化过程中形成聚合物，并与水泥水化物发生化学键合，使得水泥净浆28天抗折强度提高64％～220％，抗压强度降低1％～32％。然而该方案中制得的水泥砂浆28天抗折强度最多提高46％，对应的抗压强度降低37％，且该方法未针对更加复杂的混凝土体系进行研究，作用效果尚不明确。Patent CN111517703A "High Flexural Cement-Based Material and Preparation Method thereof" discloses a high flexural cement-based material. The invention uses initiators and accelerators to form polymers in the cement hydration process and chemically bonds with cement hydrates, so that the 28-day flexural strength of cement paste is increased by 64% to 220%, and the compressive strength is reduced by 1% to 32%. However, the 28-day flexural strength of the cement mortar prepared in this scheme is increased by up to 46%, and the corresponding compressive strength is reduced by 37%. Moreover, this method has not been studied for more complex concrete systems, and the effect is still unclear.
专利CN109250963B“一种复合增韧混凝土及其制备方法”，公开了一种复合增韧混凝土。该发明以增强增韧性能优异的氮化硼为基础材料作为混凝土添加材料，赋予混凝土良好的微观界面结合、韧性和抗疲劳性，且制备得到的混凝土28天抗压强度可以达到30-60MPa。然而氮化硼的使用不仅提高了混凝土的生产成本，同时实际工程操作性较差，进而限制其在实际工程中的推广与应 用。Patent CN109250963B "A composite toughened concrete and its preparation method" discloses a composite toughened concrete. This invention uses boron nitride, which has excellent toughening performance, as a base material as a concrete additive, giving the concrete good microscopic interface bonding, toughness and fatigue resistance, and the prepared concrete can achieve a 28-day compressive strength of 30-60MPa. However, the use of boron nitride not only increases the production cost of concrete, but also has poor operability in actual engineering, which limits its promotion and application in actual engineering. use.
发明内容Summary of the invention
针对现有混凝土外加剂的增韧效果有限，且显著影响抗压强度的问题，本发明提供一种有机-无机复合增韧材料及其在混凝土中的应用。In view of the problem that the toughening effect of existing concrete admixtures is limited and the compressive strength is significantly affected, the present invention provides an organic-inorganic composite toughening material and its application in concrete.
本发明提供了一种有机-无机复合增韧材料，包括聚合单体、交联剂、引发剂及微界面强化剂；The present invention provides an organic-inorganic composite toughening material, including a polymerizable monomer, a crosslinking agent, an initiator and a micro-interface strengthening agent;
其中引发剂占聚合单体质量的2％～7％，交联剂占聚合单体质量的0.05％～0.15％，微界面强化剂占聚合单体质量的20％～100％；The initiator accounts for 2% to 7% of the mass of the polymerized monomer, the crosslinker accounts for 0.05% to 0.15% of the mass of the polymerized monomer, and the micro-interface strengthener accounts for 20% to 100% of the mass of the polymerized monomer;
所述聚合单体选自丙烯酰胺、丙烯酸盐和甲基丙烯酸酯中的任意一种以上混合；The polymerizable monomer is selected from any one or more of acrylamide, acrylate and methacrylate;
所述微界面强化剂选自纳米硅灰石、碳酸钙晶须、硫酸钙晶须中的任意一种以上混合。The micro interface strengthening agent is selected from any one or more of nano-wollastonite, calcium carbonate whisker, and calcium sulfate whisker.
本发明所述引发剂为无机过氧化物，具体选自过硫酸铵、过硫酸钾、过硫酸钠中的任意一种以上混合。The initiator of the present invention is an inorganic peroxide, specifically selected from a mixture of any one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
所述交联剂选自N,N'-亚甲基双丙烯酰胺、2,5-二甲基-2,5二叔丁基过氧化己烷、二乙烯基苯、二异氰酸酯中的任意一种以上混合。The crosslinking agent is selected from any one or more of N,N'-methylenebisacrylamide, 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane, divinylbenzene, and diisocyanate.
本发明提供上述有机-无机复合增韧材料在混凝土中的应用，可应用于各种强度等级的混凝土，用于保证混凝土增韧效果的同时不影响抗压强度，所述有机-无机复合增韧材料中的聚合单体在引发剂和交联剂的作用下在水泥混凝土中原位聚合形成高分子聚合物，其中聚合单体占水泥质量的1％～5％。The present invention provides the application of the above-mentioned organic-inorganic composite toughening material in concrete, which can be applied to concrete of various strength grades to ensure the toughening effect of concrete without affecting the compressive strength. The polymerized monomers in the organic-inorganic composite toughening material are polymerized in situ in cement concrete under the action of an initiator and a cross-linking agent to form a high molecular polymer, wherein the polymerized monomers account for 1% to 5% of the mass of the cement.
本发明所述混凝土优选为C30混凝土。The concrete of the present invention is preferably C30 concrete.
本发明还提供了一种包含上述有机-无机复合增韧材料的混凝土的制备方法，包括以下步骤：The present invention also provides a method for preparing concrete containing the above-mentioned organic-inorganic composite toughening material, comprising the following steps:
(1)聚合单体和交联剂加水混合搅拌至完全溶解得到溶液Ⅰ，引发剂单独加水搅拌至完全溶解得到溶液Ⅱ，微界面强化剂单独加水搅拌成悬浮液Ⅲ；(1) adding water to the polymerization monomer and the cross-linking agent, stirring until completely dissolved to obtain solution I, adding water to the initiator alone, stirring until completely dissolved to obtain solution II, and adding water to the micro-interface strengthener alone, stirring to obtain suspension III;
(2)将水泥、细骨料和粗骨料倒入混凝土搅拌机中混合5～10分钟得到混合物；(2) pouring cement, fine aggregate and coarse aggregate into a concrete mixer and mixing for 5 to 10 minutes to obtain a mixture;
(3)向步骤(2)中所得的混合物中加水、步骤(1)所得的三个溶液及混凝土外加 剂，搅拌3～9分钟，制得本发明所述混凝土。(3) Add water, the three solutions obtained in step (1) and the concrete to the mixture obtained in step (2); The agent is added and stirred for 3 to 9 minutes to obtain the concrete of the present invention.
本发明所述混凝土中的水泥优强度等级32.5及以上的硅酸盐水泥、普通硅酸盐水泥、白色硅酸盐水泥中的任意一种以上混合；The concrete of the present invention is a mixture of any one or more of Portland cement, ordinary Portland cement and white Portland cement with an excellent strength grade of 32.5 or above;
本发明所述混凝土中的细骨料优选粒径0.075～4.75mm的连续级配砂，选自石英砂、河砂、石榴石砂、高强机制砂中的任意一种以上混合；The fine aggregate in the concrete of the present invention is preferably a continuously graded sand with a particle size of 0.075 to 4.75 mm, selected from any one or more of quartz sand, river sand, garnet sand, and high-strength machine-made sand;
本发明所述混凝土中的粗骨料优选花岗岩、辉绿岩、玄武岩、石灰岩中的任意一种，颗粒粒径为4.75～9.5mm；The coarse aggregate in the concrete of the present invention is preferably any one of granite, diabase, basalt and limestone, and the particle size is 4.75-9.5 mm;
本发明所述混凝土中的混凝土外加剂优选聚羧酸减水剂、有机硅类消泡剂、聚醚类消泡剂中的任意一种以上混合。The concrete admixture in the concrete of the present invention is preferably a mixture of any one or more of a polycarboxylate water reducer, an organosilicon defoamer, and a polyether defoamer.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明通过聚合物单体在引发剂及交联剂下的原位聚合和微界面强化剂的组合作用，有效提升混凝土的韧性；(1) The present invention effectively improves the toughness of concrete through the combined action of in-situ polymerization of polymer monomers under the presence of an initiator and a cross-linking agent and a micro-interface strengthener;
(2)采用本发明的有机-无机复合增韧材料，聚合单体在引发剂和交联剂的作用下在水泥混凝土中原位聚合形成的聚合物网状结构与混凝土各组分粘结在一起，显著提高混凝土的抗弯应力，减少裂缝的产生；微界面强化剂可以优化基体和骨料之间的界面过渡区，发生裂缝偏转现象，使得28天的抗压强度基本不损失；(2) The organic-inorganic composite toughening material of the present invention is used. The polymer network structure formed by the in-situ polymerization of the polymer monomer in the cement concrete under the action of the initiator and the cross-linking agent is bonded together with the various components of the concrete, which significantly improves the bending stress of the concrete and reduces the generation of cracks; the micro-interface strengthener can optimize the interface transition zone between the matrix and the aggregate, causing crack deflection, so that the 28-day compressive strength is basically not lost;
(3)采用本发明所述复合增韧材料制得的混凝土在提高抗弯应力及断裂能的同时，不影响或不降低抗压强度，改善现有混凝土材料抗折强度低、韧性差等问题；(3) The concrete made by using the composite toughening material of the present invention improves the bending stress and fracture energy without affecting or reducing the compressive strength, thereby improving the problems of low flexural strength and poor toughness of existing concrete materials;
(4)采用本发明技术制得的C30混凝土的抗弯应力可提高约40％，断裂能可提高约103％。(4) The bending stress of C30 concrete produced by the technology of the present invention can be increased by about 40%, and the fracture energy can be increased by about 103%.
具体实施方式Detailed ways
为了更充分的解释本发明的实施，提供有机-无机复合增韧材料制备混凝土的实施例。这些实施实例仅仅是解释，而不是限制本发明的范围。In order to more fully explain the implementation of the present invention, examples of preparing concrete with organic-inorganic composite toughening materials are provided. These examples are only for explanation, and do not limit the scope of the present invention.
实施例1Example 1
一种有机-无机复合增韧材料，包括聚合单体、交联剂、引发剂及微界面强化剂； An organic-inorganic composite toughening material, comprising a polymer monomer, a cross-linking agent, an initiator and a micro-interface strengthening agent;
所述聚合单体为丙烯酰胺；The polymerizable monomer is acrylamide;
所述微界面强化剂为纳米硅灰石；The micro-interface strengthening agent is nano-wollastonite;
所述引发剂为过硫酸铵；The initiator is ammonium persulfate;
所述交联剂为N,N'-亚甲基双丙烯酰胺。The cross-linking agent is N,N'-methylenebisacrylamide.
实施例2Example 2
一种有机-无机复合增韧材料，包括聚合单体、交联剂、引发剂及微界面强化剂；An organic-inorganic composite toughening material, comprising a polymerizable monomer, a crosslinking agent, an initiator and a micro-interface strengthening agent;
所述聚合单体为丙烯酸盐；The polymerizable monomer is acrylate;
所述微界面强化剂为碳酸钙晶须；The micro interface strengthening agent is calcium carbonate whisker;
所述引发剂为过硫酸钾；The initiator is potassium persulfate;
所述交联剂为2,5-二甲基-2,5二叔丁基过氧化己烷。The cross-linking agent is 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane.
实施例3Example 3
一种有机-无机复合增韧材料，包括聚合单体、交联剂、引发剂及微界面强化剂；An organic-inorganic composite toughening material, comprising a polymer monomer, a cross-linking agent, an initiator and a micro-interface strengthening agent;
所述聚合单体为甲基丙烯酸酯；The polymerizable monomer is methacrylate;
所述微界面强化剂为硫酸钙晶须；The micro interface strengthening agent is calcium sulfate whisker;
所述引发剂为过硫酸钠；The initiator is sodium persulfate;
所述交联剂由二乙烯基苯、二异氰酸酯按质量比1:1混合。The crosslinking agent is a mixture of divinylbenzene and diisocyanate in a mass ratio of 1:1.
实施例4Example 4
一种有机-无机复合增韧材料，包括聚合单体、交联剂、引发剂及微界面强化剂；An organic-inorganic composite toughening material, comprising a polymerizable monomer, a crosslinking agent, an initiator and a micro-interface strengthening agent;
所述聚合单体为丙烯酰胺；The polymerizable monomer is acrylamide;
所述微界面强化剂为纳米硅灰石；The micro-interface strengthening agent is nano-wollastonite;
所述引发剂为过硫酸铵；The initiator is ammonium persulfate;
所述交联剂为N,N'-亚甲基双丙烯酰胺。The cross-linking agent is N,N'-methylenebisacrylamide.
应用实施例 Application Examples
各实施例及对比例制备的混凝土中各组分的重量份数见表1所示。The weight percentages of the various components in the concrete prepared in the various embodiments and comparative examples are shown in Table 1.
各实施例及对比例中的“水泥”为P·II52.5硅酸盐水泥。The "cement" in each embodiment and comparative example is P·II52.5 silicate cement.
各实施例及对比例中的“细骨料”为河砂，粒径为0.075～4.75mm连续级配砂。The "fine aggregate" in each embodiment and comparative example is river sand with a particle size of 0.075-4.75 mm continuously graded sand.
各实施例及对比例中的“粗骨料”为石灰岩，颗粒粒径为4.75～9.5mm。The "coarse aggregate" in each embodiment and comparative example is limestone, and the particle size is 4.75-9.5 mm.
各实施例及对比例中的“混凝土外加剂”为聚羧酸类高性能减水剂和有机硅类消泡剂，对比例2和3中混凝土掺入的微界面强化剂为纳米硅灰石，对比例4～7中聚合单体为丙烯酰胺，对比例5～7中引发剂为过硫酸铵，对比例6和7中交联剂为N,N'-亚甲基双丙烯酰胺。The "concrete admixtures" in each embodiment and comparative example are polycarboxylic acid high-performance water reducing agent and silicone defoaming agent, the micro-interface strengthener added to the concrete in comparative examples 2 and 3 is nano-wollastonite, the polymerization monomer in comparative examples 4 to 7 is acrylamide, the initiator in comparative examples 5 to 7 is ammonium persulfate, and the cross-linking agent in comparative examples 6 and 7 is N,N'-methylenebisacrylamide.
表1各实施例及对比例中混凝土组分含量
Table 1 Concrete component contents in various embodiments and comparative examples
对比例1为基础混凝土，没有掺入复合增韧材料中的任一组分。Comparative Example 1 is a basic concrete without any component of the composite toughening material added.
对比例2和3中掺入微界面强化剂，没有掺入聚合单体、引发剂及交联剂。In Comparative Examples 2 and 3, a micro-interface strengthener is added, but no polymerization monomer, initiator or cross-linking agent is added.
对比例4中中聚合单体，没有掺入引发剂、交联剂及微界面强化剂。In Comparative Example 4, the polymerized monomers were not mixed with initiators, cross-linking agents, and micro-interface strengtheners.
对比例5中掺入聚合单体和引发剂，没有掺入交联剂和微界面强化剂。In Comparative Example 5, polymerization monomers and initiators are added, but cross-linking agents and micro-interface strengtheners are not added.
对比例6中掺入聚合单体、引发剂及交联剂，没有掺入微界面强化剂。In Comparative Example 6, polymerization monomers, initiators and cross-linking agents were added, but no micro-interface strengthener was added.
对比例7中提高聚合单体和引发剂用量。In Comparative Example 7, the amounts of polymerization monomer and initiator were increased.
实施例2中提高过引发剂用量。 In Example 2, the amount of initiator used is increased.
实施例3中提高微界面强化剂用量。In Example 3, the dosage of the micro-interface strengthening agent is increased.
上述对比例1-7和实施例1-4中的材料在制备时，先将聚合单体和交联剂加水混合搅拌，引发剂单独加水搅拌，微界面强化剂单独加水搅拌成悬浮液，将水泥、细骨料和粗骨料在卧轴式或立轴行星式强制搅拌机中混合5分钟，接着向所得的混合物中加入上述三种溶液、减水剂和消泡剂搅拌三分钟，制得所述混凝土。将拌合物进行新拌性能测试后浇筑入模24h折模，放入标准养护环境养护3天、7天和28天后测试综合性能。When preparing the materials in the above-mentioned comparative examples 1-7 and examples 1-4, firstly, the polymerized monomer and the crosslinking agent are mixed with water and stirred, the initiator is separately mixed with water and stirred, and the micro-interface strengthener is separately mixed with water and stirred into a suspension, and the cement, fine aggregate and coarse aggregate are mixed in a horizontal shaft or vertical shaft planetary forced mixer for 5 minutes, and then the above-mentioned three solutions, water reducer and defoamer are added to the obtained mixture and stirred for three minutes to obtain the concrete. After the mixture is subjected to the fresh mix performance test, it is poured into the mold for 24 hours and the mold is folded, and the comprehensive performance is tested after being placed in a standard curing environment for 3 days, 7 days and 28 days.
用上述对比例1-7和实施例1-4中的C30混凝土，进行力学性能的对比试验(以对比例1为基准，规定其力学性能为100％，其余例的力学性能依照基准变化)，试验结果如下：The C30 concrete in the above-mentioned comparative examples 1-7 and embodiments 1-4 was used to conduct a comparative test of mechanical properties (taking comparative example 1 as the benchmark, its mechanical properties were set as 100%, and the mechanical properties of the other examples were changed according to the benchmark). The test results are as follows:
表2各实施例中的C30混凝土力学性能
Table 2 Mechanical properties of C30 concrete in various examples
从表2中的试验结果可以看到，将本发明的有机-无机复合增韧材料应用于混凝土中，原位聚合形成的网状结构与混凝土各组分粘结在一起，无机微界面强化剂可以优化基体和骨料之间的界面过渡区，显著提高混凝土的韧性，从而使混凝土不仅保持28天的抗压强度基本持平，同时极大地提高混凝土的抗弯应力，和断裂能，有利于混凝土韧性的提升，具有显著的应用推广价值。From the test results in Table 2, it can be seen that when the organic-inorganic composite toughening material of the present invention is applied to concrete, the network structure formed by in-situ polymerization is bonded to the various components of the concrete, and the inorganic micro-interface strengthener can optimize the interface transition zone between the matrix and the aggregate, significantly improving the toughness of the concrete, so that the concrete not only maintains the compressive strength of the concrete for 28 days basically the same, but also greatly improves the bending stress and fracture energy of the concrete, which is beneficial to the improvement of the toughness of the concrete and has significant application and promotion value.
对比例1为基准C30混凝土，具有相对较低的抗弯应力和相对较高的抗压强度。Comparative Example 1 is a benchmark C30 concrete, which has relatively low flexural stress and relatively high compressive strength.
对比例2中引入微界面强化剂后，有利于混凝土抗压强度的提高；并且早期断裂能明显提升，但后期基本与对比例1相持平。 The introduction of micro-interface strengthener in Comparative Example 2 is beneficial to the improvement of the compressive strength of concrete; and the early fracture energy is significantly improved, but in the later stage it is basically the same as that of Comparative Example 1.
对比例3中继续引入微界面强化剂后，混凝土的抗压强度进一步提高；抗弯应力有不同程度的降低，但同样的早期断裂能显著提升，后期基本与对比例1持平。After the micro-interface strengthener was further introduced in Comparative Example 3, the compressive strength of the concrete was further improved; the flexural stress was reduced to varying degrees, but the early fracture energy was significantly improved, and the later period was basically the same as that of Comparative Example 1.
对比例4中引入聚合单体后，混凝土的抗弯应力和抗压强度均呈现降低趋势，3天和28天断裂能有所提升，7天断裂能有所降低。After the polymerized monomer was introduced in Comparative Example 4, the flexural stress and compressive strength of the concrete showed a decreasing trend, the 3-day and 28-day fracture energies were increased, and the 7-day fracture energy was decreased.
对比例5中引入聚合单体和引发剂后，引发剂使聚合单体在基体中发生原位聚合，抗弯应力有所提升，断裂能大幅提升；但抗压强度相对于比例4有所提高，但与比例1相比，仍存在下降趋势。After the polymerizable monomer and initiator are introduced in Comparative Example 5, the initiator causes the polymerizable monomer to undergo in-situ polymerization in the matrix, the bending stress is improved, and the fracture energy is greatly improved; however, the compressive strength is improved relative to Comparative Example 4, but compared with Comparative Example 1, there is still a downward trend.
对比例6和7中引入聚合单体、引发剂和交联剂后，同样的提高混凝土的抗弯应力，但抗压强度有所降低。In comparative examples 6 and 7, after the polymerization monomer, initiator and cross-linking agent were introduced, the bending stress of the concrete was also improved, but the compressive strength was reduced.
实施例1～4中，随着聚合单体、引发剂、交联剂及微界面强化剂的组合作用，有效提升C30混凝土的韧性，3天和28天的最大抗弯应力分别提升63％和42％；3天和28天最大断裂能提升了约3.5倍和1.2倍；且C30混凝土28天的抗压强度与对比例1基本持平。In Examples 1 to 4, with the combined effects of the polymerization monomer, initiator, cross-linking agent and micro-interface strengthener, the toughness of C30 concrete is effectively improved, and the maximum bending stress at 3 days and 28 days is increased by 63% and 42% respectively; the maximum fracture energy at 3 days and 28 days is increased by about 3.5 times and 1.2 times; and the compressive strength of C30 concrete at 28 days is basically the same as that of Comparative Example 1.
本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下本发明还有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。 The present invention is not limited by the above embodiments. The above embodiments and descriptions are only for illustrating the principles of the present invention. The present invention may be subjected to various changes and modifications without departing from the spirit and scope of the present invention. These changes and modifications all fall within the scope of the present invention claimed for protection.

Claims (9)

  1. 一种有机-无机复合增韧材料，其特征在于，该有机-无机复合增韧材料包括聚合单体、交联剂、引发剂及微界面强化剂；An organic-inorganic composite toughening material, characterized in that the organic-inorganic composite toughening material comprises a polymerizable monomer, a cross-linking agent, an initiator and a micro-interface strengthener;
    其中引发剂占聚合单体质量的2％～7％，交联剂占聚合单体质量的0.05％～0.15％，微界面强化剂占聚合单体质量的20％～100％；The initiator accounts for 2% to 7% of the mass of the polymerized monomer, the crosslinker accounts for 0.05% to 0.15% of the mass of the polymerized monomer, and the micro-interface strengthener accounts for 20% to 100% of the mass of the polymerized monomer;
    所述聚合单体选自丙烯酰胺、丙烯酸盐和甲基丙烯酸酯中的任意一种以上混合；The polymerizable monomer is selected from any one or more of acrylamide, acrylate and methacrylate;
    所述微界面强化剂选自纳米硅灰石、碳酸钙晶须、硫酸钙晶须中的任意一种以上混合。The micro interface strengthening agent is selected from any one or more of nano-wollastonite, calcium carbonate whisker, and calcium sulfate whisker.
  2. 根据权利要求1所述的一种有机-无机复合增韧材料，其特征在于，所述引发剂为无机过氧化物。The organic-inorganic composite toughening material according to claim 1, characterized in that the initiator is an inorganic peroxide.
  3. 根据权利要求2所述的一种有机-无机复合增韧材料，其特征在于，所述引发剂选自过硫酸铵、过硫酸钾、过硫酸钠中的任意一种以上混合。The organic-inorganic composite toughening material according to claim 2 is characterized in that the initiator is selected from a mixture of any one or more of ammonium persulfate, potassium persulfate, and sodium persulfate.
  4. 根据权利要求2所述的一种有机-无机复合增韧材料，其特征在于，所述交联剂选自N,N'-亚甲基双丙烯酰胺、2,5-二甲基-2,5二叔丁基过氧化己烷、二乙烯基苯、二异氰酸酯中的任意一种以上混合。The organic-inorganic composite toughening material according to claim 2 is characterized in that the crosslinking agent is selected from a mixture of any one or more of N,N'-methylenebisacrylamide, 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane, divinylbenzene, and diisocyanate.
  5. 一种权利要求1至4任一项所述有机-无机复合增韧材料在混凝土中的应用。A use of the organic-inorganic composite toughening material according to any one of claims 1 to 4 in concrete.
  6. 根据权利要求5所述的应用，其特征在于，上述有机-无机复合增韧材料应用于各种强度等级的混凝土中，所述有机-无机复合增韧材料中的聚合单体在引发剂和交联剂的作用下在水泥混凝土中原位聚合形成高分子聚合物，其中聚合单体占水泥质量的1％～5％。The use according to claim 5 is characterized in that the above-mentioned organic-inorganic composite toughening material is applied to concrete of various strength grades, and the polymerization monomers in the organic-inorganic composite toughening material are in situ polymerized in cement concrete under the action of an initiator and a cross-linking agent to form a high molecular polymer, wherein the polymerization monomers account for 1% to 5% of the mass of the cement.
  7. 根据权利要求6所述的应用，其特征在于，所述混凝土为C30混凝土。The use according to claim 6, characterized in that the concrete is C30 concrete.
  8. 根据权利要求6或7所述的应用，其特征在于，包含上述有机-无机复合增韧材料的混凝土的制备方法，包括以下步骤：The use according to claim 6 or 7 is characterized in that the method for preparing concrete containing the above-mentioned organic-inorganic composite toughening material comprises the following steps:
    (1)聚合单体和交联剂加水混合搅拌至完全溶解得到溶液Ⅰ，引发剂单独加水搅拌至完全溶解得到溶液Ⅱ，微界面强化剂单独加水搅拌成悬浮液Ⅲ；(1) adding water to the polymerization monomer and the cross-linking agent, stirring until completely dissolved to obtain solution I, adding water to the initiator alone, stirring until completely dissolved to obtain solution II, and adding water to the micro-interface strengthener alone, stirring to obtain suspension III;
    (2)将水泥、细骨料和粗骨料倒入混凝土搅拌机中混合5～10分钟得到混合 物；(2) Pour cement, fine aggregate and coarse aggregate into a concrete mixer and mix for 5 to 10 minutes to obtain a mixed things;
    (3)向步骤(2)中所得的混合物中加水、步骤(1)所得的三个溶液及混凝土外加剂，搅拌3～9分钟，制得所述混凝土。(3) adding water, the three solutions obtained in step (1) and a concrete admixture to the mixture obtained in step (2), and stirring for 3 to 9 minutes to obtain the concrete.
  9. 根据权利要求8所述的应用，其特征在于，所述水泥选自强度等级32.5及以上的硅酸盐水泥、普通硅酸盐水泥、白色硅酸盐水泥中的任意一种以上混合；The use according to claim 8 is characterized in that the cement is selected from any one or more of Portland cement, ordinary Portland cement, and white Portland cement with a strength grade of 32.5 or above;
    所述细骨料选自粒径0.075～4.75mm的连续级配砂，选自石英砂、河砂、石榴石砂、高强机制砂中的任意一种以上混合；The fine aggregate is selected from continuously graded sand with a particle size of 0.075 to 4.75 mm, and is selected from a mixture of any one or more of quartz sand, river sand, garnet sand, and high-strength machine-made sand;
    所述粗骨料选自花岗岩、辉绿岩、玄武岩、石灰岩中的任意一种，颗粒粒径为4.75～9.5mm；The coarse aggregate is selected from any one of granite, diabase, basalt and limestone, and the particle size is 4.75-9.5 mm;
    所述混凝土外加剂选自聚羧酸减水剂、有机硅类消泡剂、聚醚类消泡剂中的任意一种以上混合。 The concrete admixture is selected from a mixture of any one or more of a polycarboxylate water reducer, an organosilicon defoamer, and a polyether defoamer.
PCT/CN2023/108309 2022-10-21 2023-07-20 Organic-inorganic composite toughening material and use thereof in concrete WO2024082735A1 (en)

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